3-amino-2-cyclobuten-1-one compounds and process for their preparation



3,408,344 Patented Oct. 29, 1968 3,408,344 S-AMINO-Z-CYCLOBUTEN-l-ONE COMPOUNDS AND PROCESS FOR THEIR PREPARATION James C. Martin, Kingsport, Tenn., assignor to Eastman Kodak 'Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Nov. 23, 1964, Ser. No. 413,281

7 Claims. (Cl. 260-239) ABSTRACT OF THE DISCLOSURE 3-amino-2-cyclobuten-l-one compounds are prepared by reacting a 3-alkoxy-2-cyclobuten-l-one compound with certain organic amines. The 3-amino-2-cyclobuten-l-one compounds are useful, for example, as corrosion inhibitors for ferrous alloys and as chemical intermediates in v the production of other useful compounds such as cyanine dyes.

This invention relates to novel chemical compounds and to their preparation. More particularly, it relates to novel 3-amin0-2-cyclobuten-1-one compounds and to novel methods for preparing them.

The novel 3-amino-2-cyclobuten-l-one compounds have the formulas:

wherein R represents a hydrogen atom or a lower alkyl radical (i.e. having from 1 to 4 carbon atoms), R, and R each represents an alkyl radical, R and R each represents a hydrogen atom, an alkyl radical, a cyanoalkyl radical, a hydroxyalkyl radical or a monocyclic and nucleus, X represents a radical or a radical, n represents a whole number from 2 to 6, and wherein collectively, can be the radical of a cyclic monoamine. Preferably, R and R have from 1 to 4 carbon atoms although they can have from 1 to 8, or higher, carbon atoms. Similarly, when either R or R (or both) is an alkyl radical the alkyl radical preferably has from 1 to 4 carbon atoms. although it can have from 1 to 8, or higher, carbon atoms.

The new 3amino-2-cyclobuten-l-one compounds of the invention having the Formula I are prepared by reacting the corresponding 3-alkoxy-2-cyclobuten-l-one compounds having the formula:

RzO-(i-b-R,

4 with an amine having the formula:

Bil-Rs wherein R represents a lower alkyl radical and 11, R R R4, R5, R5 and i t I collectively, have the meaning previously assigned to them. The new 3-amino-2-cyclobuten-l-one compounds of the invention having the Formula II are prepared by reacting the 3-alkoxy-2-cyclobuten-l-one compounds having the Formula IV with an alkylene diamine having the formula:

(VI) H NYNH wherein Y represents a radical or a straight chain alkylene radical having 2 to 6 carbon atoms.

The new 3-amino-2-cyclobuten-l-one compounds of the invention having the Formula III are prepared by reacting the 3alkoxy-2-cyclobuten-l-one compounds having the Formula IV with piperazine.

Van Daalen, Kraak and Arens have reported in Rec. trav. chim. 80, 813, 817, 818 (1961) that when 2-nbutoxy 1,3 dimethylcyclobut-2-ene-4-one was refluxed with aniline the anil of pentane-B-one, the butyl ester of phenylcarbamic acid, butanol and N,N -diphenylurea where produced. None of these products was produced in the process of the present invention.

The new 3-amino-2-cyclobuten-l-one compounds of the invention are prepared in accordance 'with the process of the invention by mixing the amine or ammonia reactant with the 3-alkoxy-2-cyclobuten-l-one reactant, with or without a solvent, and isolating the desired product by distillation or recrystallization. Suitable solvents include water, alcohols, esters, nitriles, aliphatic or aromatic hydrocarbons, chlorinated hydrocarbons and ethers. Suitable reaction temperatures are in the range of about 10 C. to C. Higher temperatures within this range are preferably employed when a less reactive amine reactant is involved. For reasons of economy the reactants are preferably used in the molar ratio of 1:1 but other ratios can be used if desired. An excess of either reactant can be used. The use of a solvent is generally preferred.

Suitable solvents are materials that serve to dissolve the reagents involved in the process but which do not react with them. Suitable inert solvents include, for ex ample, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylketone, methylisobutylketone, hexane, naphtha, isooctane, benzene, toluene, xylene, carbon tetrachloride, chloroform, tetrachloroethane, acetonitrile, isobutyronitrile, ethyl acetate, butyl acetate, ethyl alcohol, propyl alcohol, butyl alcohol, etc., and di-polar aprotic solvents such as dimethyl formamide, ethylene carbonate, sulfolane, etc.

R and R each typically represents an alkyl radical having 1 to 8 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, etc. although they can be a higher alkyl radical such as nonyl and decyl, for example. Preferably R and R each re re cmsa qwe .a lvrad re-a. f to .4... r .on.mwm aqc s 9 1a.Yar n33 0B iestrumemamued.peak atoms. i '(in c.p.s. relative to water as an external standard):

When either R or R (or both) is an alkyl radical H CH3 each typically represents an alkyl radical having 1 t0 8 carbon atoms such as methyl, ethyl, propyl, isopropyl, 5 C 163, /G\ butyl, sec. butyl, tert. butyl, pentyl, hexyl, heptyl, octyl, CH3 y y althoughithey can be a higher alkyl The relative area ratios were 2:116. radical such ,as nonyl and decyl, for example. When either EXAMPLE 2 R or R (orboth) is an alkyl radical preferably each represents a lower alkyl radical, i.e., of 1 to 4 carbon atoms. 10 i g w Ammonia, methylamine, ethylamine,,propylamine, iso- C H '0' b; C( CH) 1 propylamine, butylamine, amylamine, hexylamine, hep- Fff'*$= tylamine,.octylamine, nonylamine, decylamine, fi-cyano- N- CC(CH ethylamine, 'y-cyanopropylamine, B-hydroxyethylamine, 'yrhydroxypropylamine. dimethylamine, diethylamine, di- A solution of 40, g. (0.285 mole) of 3-et hoxy-4 ,4 -dipropylam ne, dibutylamine, dihexylamine, dioctylaminc, methyl-2-cyclobuten l-one and 24.3 g. (O.285 mole) of didecyla'rnine, aniline, p-methylaniline, p-methoxyaniline, pipe'ridine in 100 ml.. of benzene was refluxed for 5 hours. p -ethoxyaniline, diphenylam ine, di(p-methoxyph y Mostof the benzene was removed. by distillation'at 'atamine, di(p-methylphenyl)amine, morpholine, piperidine, niospheric pressure.v The residue crystallized .oZnYCooling pyrrolidine, bicyclo[3.2.2];3-azanonane, N-methylaniline, t0 ,gi've,5 0.4 g.' (98%) of crude 3-piperidino 4,4-dimeth- N-ethylaniline, N-butylaniline, N-fi-hydroxyethylaniline, yl-2-cy clobuten-l-one. Upon being recrystallized two N-z -hydroxypropylaniline,- N B -.cyanoethy1aniline and times from a mixture of benzene and hexanethe 3- piper- N- -cyanopropylaniline, for example, are illustrative. of idino-4,4-dimethyl-2-cyclobuten- 1rone product melted a the amines used in the preparation of the novel 3-amin0- 104 .C.lO4.5 C. 2-cyclobuten-l-one compounds of the invention. Analysis-Calcd. for C H NO: C, 73.9; H, 9.5; N, The following examples illustrate the invention: 7.8. Found: C, 74.0; H, 9.8; N, 7.7. v

The n.m.r. spectrum agreed with the structure assigned to this material. EXAMPLE 1 EXAMPLE 3 Ito-0:0 HCC=0 I l +NH4OH Ll I A solution of 42 g. (0.3 mole) of 3-ethoxy-'4,4-d1- methyl-Z-cyclobuten-l-one and 27.6 g. (0.3 mole) ofaniline in 100 ml. of acetonitrile was refluxed for 60 hours. A mixture of 20 (0.14 mole) of The infrared spectrum of the reaction solution indicated methyl-Z-cyclobuten-l-one and 40 ml. of 28% ammothat i Startling matenal was gone a bands i nium hydroxide was stirred at room temperature for 4 actgnsnc of t ehproduct z g t essolunon was ta hours. The resulting solid was isolated by filtration, ig e tofgwe of a g f washed with water, and dried in air. There was obtained i resl thecrysta lianon mm amine gave 13.9 g. (89%) of 3-amino-4,4-dimethyl-Z-cyclobuten-lhavmg a one, M.P. 213 C. (decomposition). An analytical sam- 106 f.

ple was recrystallized from ethanol; M.P. 213 C. (dec.). Analysis.Calcd. for C H NO: C, 64.9; H, 8.1; N, 12.6. Found: C, 65.0; H, 8.3; N, 12.6.

The n.m.r. spectrum of this material, measured at 40 EXAMPLE 4 Under the general conditions used in Example 3, the amines and 3-alkoxy-2-cyclobuten-l-one compoundsgiv the products shown in the following tabulation.

Amine Oyclobutenone Product p-Methoxyaniline 3-ethoxy-4,4-dirnethyl-2- 3-(p-methoxyanilino)-4,4-dimethyl-Z-cyclo-buten-lcyclobuten-l-one. one. (Di-r-cyanoethyD-amine do 3-(di-fl-eyanoethyl)-amino-4,4-dirnethyl-2 cyclobuten-l-one.

do HCC=O S NI-I (Bicyclo[3.2.21-3-azan0nauc) cyclobuten-l-one.

i l l aam fl'Hydroxyethylamine 3-butoxy-4,4-diethyl-2- 3-(B-hydroxyethylumiuo)4,4-diethyl-2-cyclobuten-1- cyclobuten-l-one. one. 7

3-ethoxy-2,4,4-tri- CH;CO=O S N11 methyl-Z-cyclobutenl-onc. S N-C-C (CH3): (Pyrrolidmc) (3-pyrrolidino-2,4,4-trimetl1yl-2-cyclobuten-l-one).

1I;N( CH1) BNHZ 3-ethoxy-4,4-dimethyl-2- O=GCH ITO-0 0 cyclobuten-l-one.

H H (CHa)2CCN(CHz)tN-C-C(CH V Amine Cyclobutenoue Product Piperazine d O=COH TIC-0:0

(CH3)2(IZCHIN S N-CC (C1192 Piperidine 3-ethoxy-4,4-dibutyl- 3-piperidino-4,4 dibutyI-Z-cyclobuten-l-one.

2-cyclobuten-1-oue.

Pyirolidlne do 3-pyrrol1dino-4,4dibutyl-2-cyc1obuten-l-one.

B-Cyanoethylamine 3-ethoxy-4,4-dipropyl- 3(fl-cya110ethylamino)-4,4dipropyl-2-cyclobuten- 2-cyclobuten-1-one. l-one.

EXAMPLE 5 EXAMPLE 6 A mixture of 70 g. (0.5 mole) of 3-ethoxy-4,4-dimethyl- 2m a)2C= =O H- 0 2-cyclobuten-1-one and 62 g. (2.0 moles) of methylamine is heated in an autoclave at 150 for 6 hrs. Distillation of 021150 the reaction product through a IO-in. packed column gives 3 a good yield of 3-methylamino-4,4-dimethyl-2-cyclobuten- To a Stirred Solution of 98 (L4 moles) of ethoxy acetylene in 300 ml. of hexane was added 98 g. (1.4 By the of an equivalent amount ethylamme. moles) of dimethylketene. The reaction was slowly exo propylamme propylanime butylamme respectliely thermic, and an ice bath was used to keep the temperam Place of methylamme m Examgle i' ture below 40 C. After stirring for 5 hours, the solution 4t4'dlmethyl'z'cyclobuten'l'one 3 i z gf 'gi' was distilled through a 12-inch packed column to give dlmethylz'cyclobuten'l'one i 111 g. (57%) of 3-ethoxy-4,4-dimethyl-2-cyclobuten-1- 2-cyclobuten-l-one and 3-butylam1no-4,4-d1methyl-2- one BP (2 5 mm) H 201 4583 cyclobuten-l-one, respectively, are obtained. i g C 8 68 H 8 6 Found. The 3-alkoxy-2-cyclobuten-l-one compounds used in the C 68 5 8 12 preparation of the 3-amino-2-cyclobuten-l-one compounds sig'nificant'il'lfrared maxima at 5 7 (S and 6 3 (s). of the mvemlon t descnbed m Patent The nuclear magnetic resonance spectrum zlvas in complete In accordance with US. Patent 3,288,854 the 3-alkoxya greement with the structure assigned. 2-cyclobuten-1-one compounds are prepared by cycloaddition of dialkylketenes to alkoxyacetylenes. They are EXAMPLE 7 useful chemical intermediates, for example, in the prepara- Using the same general procedure as Example 6, tion of cyanine dyes useful as Photographic Spectral f (14 moles) of ethoxyacetylene, 250 ml. of acetonitrile sitizers and esters useful as plasticizers for synthetic resins D and 98 (14 moles) of dimethylketene gave 137 and in the preparation of compounds having pharmaceu- (70%) of 1 1. tical activity. They are also useful directly as plasticizers and are stable at temperatures up to 150 C. Their ther- EXAMPLE 8 mal stability is a valuable attribute because it eliminates 40 To a Stirred Solution f 51 73 l f h formation of Y-P substihl'wd naphthol acetylene in 150 ml. of hexane at room temperature was compounds. added 92 g. (0.73 mole) of butylethylketene. Stirring was The Preparation of the alkoxycyclohhtehohe continued for 6 hours at room temperature, then the solu- Pohhds can be accomplished y mixing the dialkylkhtehe tion was refluxed for 12 hours. Distillation through a 10- with the alkoxyacetylene, with or without a solvent. Su1tinch vigreux column gave 7 g. 15% f 2. m 1-3- able solvents include both polar and nonpolar solvents g 1 1- p 33 0. such as aliphatic or aromatic hydrocarbons, ethers, chlo- 20 4 Also unreacted butylethylketene and rinated hydrocarbons, esters and nitriles. Suitable reaction id tifi d material boiling at 129432 6 mm) were temperatures are in the range of about 0 to 150 C. i Higher ilempelamfes Within this range are Preferably Production of a novel ketene dimer is illustrated by ployed for the less reactive ketenes. For reasons of the next 1 economy the reactants are preferably used in the molar EXAMPLE 9 ratio of 1:1 but other ratios can be used if desired. H

The dialkylketenes used are of the type, R R =Q H20 wherein R and R are alkyl groups. It will be understood 0 H H+ that for convenience, the term dialkylketene is used in 2 5 3 its broad sense to include those compounds in which R a and R are alkylene radicals that form a ring with the (V11) carbon to which they are attached. Examples of suitable H H H 0 dialkylketenes include: dimethylketene, ethylmethylketene, methylpropylketene, butylethylketene, diethyl- HO CH3 0 ketene, pentamethyleneketene, hexamethyleneketne, ethyl- (1H3 O isobutylketene and the like. 3 The alkoxyacetylenes used are of the type, (VH1) (IX) 3-ethoxy-4,4-dimethyl-2-cyclobuten-l-one (VII), as produced in Example 6, was subjected to hydrolysis in 5% wherein R is hydrogen or a lower alkyl radical and R hydrochloric acid solution at room temperature, giving is a lower alkyl'radical. Suitable alkoxyacetylenes have a 76% yield of 3-hydroxy-4,4-dimethyl-Z-cyclobutenone been described by Arens in Advance in Organic Chemis- (VIII), M.P. 131-1 32 C. try, R. A. Raphael et al., editors; Interscience Publishers, Analysis.Calcd. for C H O C, 64.3; H, 7.2. Found: Inc., New York, New York, 1960, pages 127-129. Typical C, 64.1; H, 7.0. examples include: ethoxyacetylene, methoxyacetylene, The infrared spectrum spectrum (KBr pellet) showed l-ethoxypropyne, l-ethoxy-l-heptyne and the like. two broad bands centered at 4.22 and 5.31,u, a sharp band The following examples illustrate the preparation of at 5.88 and broad multiple bands centered at 6.6 to 7.5,u. the 3-alkoxy-2-cyclobuten-l-one compounds having the The n.m.r. spectrum of a 20% solution in dimethyl- Formula IV. formamide was in agreement with the structure (VIII).

'7 The product (VIII) of Example 9 is the enolic form of the mixed dimer of ketene and dimethylketene, the first khown cyclobutane-type dimer (IX) involving ketene. It isa relatively strong acid (pK 2.6). It and the other mixed dimers of ketenes are valuable chemical reagents. They can be employed for a number of types of reactioris for which known dimers of ketenes have been used. They offer the advantage of producing reaction products of which the number and/ or positions of the alkyl substituentsj difier from those of the products of the known dimers of ketenes. As a consequence a method is now provided for preparing products 'nofpreviously obtainable or that were heretofore produced only by more diflicult methods.

EXAMPLE 10 Under the general conditions of Example 7, the following *ketenes -.andalkoxyacetylenes give the products shown: v

. Ketene Alkoxyacctylene Product o (C8Hl7)2C- C=O.-- HCECOC H5 CH o (CH3)IC=C=O. CHsCECOCH:

OHsO CH3):

0 (CH3)2C:C=O HCECOCJI;

i lV- O (CzH5)3C-'=C=O CrHaCECO CaHs.

C 2H5 O 0215 2 EXAMPLE 11 =O H2 OH l l 2H50- M Callso H2):

A solution of 10 g. of 3-ethoxy-4,4-dimethyl-2-cyclobuten-l-one in 75 ml. of cyclohexane was hydrogenated in an autoclave over 4 g. of 5% ruthenium on carbon catalyst at 50 C. and 1500 p.s.i. for 4 hrs. The catalyst was removed by filtration and the filtrate was evaporated to give 9.6 g. of residue. Vapor phase chromatography indicated that this residue was one component. The infrared spectrum was identical to that of 2,2-dimethyl-3- ethoxycyclobutanol, B.P. 96-97 C. at 2 mm., prepared by another procedure.

The alkoxycyclobutanols as prepared in Example 11 are useful as intermediates in the preparation of esters of various carboxylic acids, e.g., diesters of dicarboxylic acids such as adipic, azelaic or sebacic acids, which are useful as. plasticizers for synthetic resins such as poly(vinyl chloride) or cellulose acetate butyrate. The next example illustrates preparation of such a diester.

EXAMPLE 12 A mixture of 100 g. of 2,2- dimethyl-3-ethoxycyclobutanol, 200 ml. of benzene, and 80 g. of pyridine was placed in a flask which was equipped with a stirrer, reflux condenser, and dropping funnnel, and 65 g. of adipyl chloride was added slowly. The mixture was stirred three hours and filterted. The solid (pyridine hydrochloride) was washed with beznene; the combined filtrates were washed with water, stripped of solvent, and distilled in a cyclic falling film molecular still to give 63 g. of bis(2,2- dimethyl-3-ethoxycyclobutyl)adipate, B.P. 82-94 n 1.4568 1.4570.

' Analysis.-Calcd. for C H O sapon. equiv., 198 Found: sapon. equiv., 195.

The following example illustrates that the hydroxycyclobutenones can be present as the enol or keto formdepending on the solventin which they are dissolved.

EXAMPLE 13 no (om): o (011m The infrared spectrum (KBrpellet) of l3-hydroxy-4,'4f dimethyl-2- cyclob'uten-l one (prepared according to Ex-. ample 9) showed two hrba'd band's centered at 4.22 and 5.31 a sharp band at'5.88,u, and broad'mult'iple bands at 6 .6 to'7.5;i. These bands'are indicativeof the enol form (A). The infrared spectrum of a solution of this material in chloroform showed none of the bands mentionedabove, but a new sharp band at 5.70 1; This spectrum is consistent with keto form (B). The n.m.r. spectrum of a 20% solution of the compound in dime'thylfor'niamidc showed single peaks at 492 c.p.s. (eriolic ()I- I), 1's2 c.p.s. (C= CH) and 49' c.p.s. '[C(CI- I These data areindicative of the enol form (A), but thejn, m.r. spectrum of its chloroforrn solution showed only single peaks at 155 c.p.s. CH5 and 57 c.p.s. [C (CI -I indicating the keto form (B). I

The n.m.r. spectra were determined at 40 me. and peak positions are reported in cycles per second relative to tetramethylsilane as an internal standard.

EXAMPLE 14.

Under the general conditions of Example 9, the following alkoxycyclobutenones give the products 'shown. Al-

though these products are shown in the enol form, it is understood that they are convertible into the keto form.

Alkoxycyclobutenone Product C H C H3 Q1330 (OH3)2 HO (CH3):

(1211 0 -C4Hu HO- C4H9 The keto forms of the novel hydroxycyclobutenones which have a methylene group (CH in the fourmembered ring have another valuable utility. Because of the active methylene group between the two carbonyl groups these compounds can be used to prepare cyanine dyes useful as spectral sensitizers for photographic silver halide'emulsi'ons. The procedure comprises condensing the keto form of the novel compound of the formula,

' Y Hie-0 0 0=oo-R' with one of the well-known fI.C.I intermediates such as 2 13 acetanilidovinyl 3 ethylbenzoxazolium iodide, which are disclosed; e.g., in British Patent No. 344,409 and U.S. Patent No. 2,870,014. I

The reaction is carried out by heating the reactants, e.g., in equimolar proportions, in the presence of a basic condensing agent, e.g., triethylamine, and an inert diluent such as ethanol, propanol, 1,4-dioxane, etc..Temperatures from ambient temperature to the reflux temperature of thereaction' mixture can be used. The resulting dye is recovered by filtration and recrystallization. Suitable procedures aredisclosed in U.S. Patent 2,870,014 which also discloses well-known procedures by which'the cyanine 9 1" dyes formed from the aforesaid hydroxycyclobutenone compounds can be incorporated in photographic silver halide emulsions as spectralsensitizers. N The preparation of such a cyanine dye is illustrated'b'y the following example. g

EXAMPLE 15.-4 [(3 ETHYL 2 BENZOXA- ZOLINYLIDENE)ETHYLIDENE] 2,2' DIMETH- YL-l,3-CYCLOBUTANEDIONE 2,2 dimethyl 1,3 cyclobutanedione (0.56 g., 1 mol.) and 2 ,8 acetanilidovinyl 3 ethylbenzoxa zolium iodide (2.18 g., 1 mol.) and triethylamine (1.4 ml., 1 mol.+100%) were dissolved in ethanol (10 ml.) and the mixture heated under reflux for ten minutes. After chilling, the reaction mixture was diluted with chloroform (1000 ml.) and washed with several 100 ml. portions of water. After drying, the chloroform solution was chromatographed on a 12-inch column of neutral alumina 1 inch in diameter. After concentrating the desired fraction, the residue was twice recrystallized from benzene. The yield of purified dye was 1.1 g. (79%), M.P.

188l90 C. dec.

The novel alkoxycyclobutenone compounds are useful not only as chemical intermediates but can also be used directly as plasticizers for synthetic resins. The following example illustrates the use as a plasticizer.

EXAMPLE 16 Fifteen parts of 2 butyl 3 ethoxy 2 ethyl 3- cyclobuten-l-one is milled on heated rolls with 85 parts of cellulose acetate butyrate resin to give a tough plasticized resin with improved molding properties.

The examples given hereinbefore are intended to be illustrative and not limitative of the invention. It is obvious that numerous other compounds of the invention in addition to those specifically disclosed can be prepared. Thus by the use of ethylene diamine (H NCHzCHzNHz), 1,3 propane diamine (H NCH CH CH NH 1,4- butane diamine (H NCH CH CH CH NH and 1,5- pentane diamine [H N(CH NH respectively, in place of 1,6-hexane diamine [H N(CH NH in Example 4 of the formulas of the resulting products would differ from that shown in Example 4 in that the connecting linkage in the products would be Similarly, R R R R and R can represent higher alkyl groups than those specifically disclosed in the examples illustrating the invention.

The novel 3-amino-2-cyclobuten-l-one compounds of the invention are useful as corrosion inhibitors for ferrous alloys. The compounds having the Formula 1 can be converted to the corresponding 3-hydroxycyclobutenone compounds by hydrolysis. The hydrolysis can'be effected, for example, with a 5% hydrochloric acid solution. As shown hereinbefore the keto forms of the -3- hydroxycyclobutenone compounds can be used to pre pare cyanine dyes useful as spectral sensitizers for photographic silver halide emulsions.

The invention has been described in detail withparticular reference to preferred embodiments thereof, but it will be understood that variations and nrodifications can be effected within the spirit and scope of the inven- 10 tion as described 'hereinbefore and as. defined in the appended claims. v Iclaim: v

1. The cyclobutenone compounds having the formulai consisting of a hydrogen atom and a lower alkyl radical having from I to 4 carbon atoms, R, and R each represents an alkyl radical having from '1 to 10 carbon atoms, X represents a H H -NCH2 S CHa-N- radical or a with an amine having the formula:

5 HN-Ra at a temperature in the range of about 10 to about C. and recovering a product having the formula:

wherein R represents a member selected from the group consisting of a hydrogen atom and a lower alkyl radical, R represents a lower alkyl radical, R and R each represents an alkyl radical having from 1 to 10 carbon atoms, R and R each represents a member selected from the group consisting of a hydrogen atom, an alkyl radical having from 1 to 10 carbon atoms, a cyanoalkyl radical having up to 3 carbon atoms, a hydroxyalkyl radical havrng up to 3 carbon atoms, phenyl, methylphenyl, methoxyphenyl and ethoxyphenyl and wherein collectively, can be a cyclic monoamine radical selected from the group consisting of morpholine, piperidine, pyrrolidine and 3-azabicyclo [3.2.2]nonane.

7. The process according to claim 6 wherein R R ancrR ea eh represent sa member selected from; the OTHER REFERENCES 7 group consisting of a hydrogen atom and a lower alkyl H k t L: J. Or Ch OL 29 25 3 radieal and R R and R each represents a lower alkyl 1 e a g e v pp radlcah Van Daalen et a1.: Rec. Trav. Chim., vol. 80, pp 810- References Cited 5 1 19 1 UNITED STATES PATENTS 3 2 2 924 1 9 Ait et a1 260 563 ALTON ROLLINS, Primary Examine"- UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3,408,344 October 29, 1968 James C. Martin It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Column 6, lines 53 to S6, formula (VII) should appear as shown below:

Column 8, in the table, first column, the second formula should appear as shown below:

c n o C4H9 Signed and sealed this 10th day of March 1970 (SEAL) Attest:

EDWARD M.FLETCHER,JR, WILLIAM E. SCHUYLER, JR. 

